The present invention relates to electrophoretic displays using nanoparticles, that is particles having diameters substantially less than the wavelengths of visible light. The present invention also relates to nanoparticle assemblies and to displays incorporating such assemblies. In one aspect this invention relates to nanoparticle assemblies and to displays in which one nanoparticle is linked to a second nanoparticle or other object by means of a linking moiety, the electrical conductivity of which can be varied.
Electrophoretic displays have been the subject of intense research and development for a number of years. Such displays use a display medium comprising a plurality of electrically charged particles suspended in a fluid. Electrodes are provided adjacent the display medium so that the charged particles can be moved through the fluid by applying an electric field to the medium. In one type of such electrophoretic display, the medium comprises a single type of particle having one optical characteristic in a fluid which has a different optical characteristic. In a second type of such electrophoretic display, the medium contains two different types of particles differing in at least one optical characteristic and in electrophoretic mobility; the particles may or may not bear charges of opposite polarity. The optical characteristic which is varied is typically color visible to the human eye, but may, alternatively or in addition, be any one of more of reflectivity, retroreflectivity, luminescence, fluorescence, phosphorescence, or (in the case of displays intended for machine reading) color in the broader sense of meaning a difference in absorption or reflectance at non-visible wavelengths.
Electrophoretic displays can be divided into two main types, namely unencapsulated and encapsulated displays. In an unencapsulated electrophoretic display, the electrophoretic medium is present as a bulk liquid, typically in the form of a flat film of the liquid present between two parallel, spaced electrodes. Such unencapsulated displays typically have problems with their long-term image quality which have prevented their widespread usage. For example, particles that make up such electrophoretic displays tend to cluster and settle, resulting in inadequate service-life for these displays.
An encapsulated, electrophoretic display differs from an unencapsulated display in that the particle-containing fluid is not present as a bulk liquid but instead is confined within the walls of a large number of small capsules. Encapsulated displays typically do not suffer from the clustering and settling failure mode of traditional electrophoretic devices and provides further advantages, such as the ability to print or coat the display on a wide variety of flexible and rigid substrates.
For further details regarding encapsulated electrophoretic displays, the reader is referred to U.S. Pat. Nos. 5,930,026; 5,961,804; 6,017,584; 6,067,185; 6,118,426; 6,120,588; 6,120,839; 6,124,851; 6,130,773; 6,130,774; 6,172,798; 6,177,921; 6,232,950; 6,249,721; 6,252,564; 6,262,706; 6,262,833; 6,300,932; 6,312,304; 6,312,971; 6,323,989; 6,327,072; 6,376,828; 6,377,387; 6,392,785; 6,392,786; 6,413,790; 6,422,687; 6,445,374; 6,445,489; and 6,459,418; and U.S. Patent Applications Publication Nos. 2001/0045934; 2002/0019081; 2002/0021270; 2002/0053900; 2002/0060321; 2002/0063661; 2002/0063677; 2002/0090980; 2002/106847; 2002/0113770; 2002/0130832; and 2002/0131147, and International Applications Publication Nos. WO 99/53373; WO 99/59101; WO 99/67678; WO 00/05704; WO 00/20922; WO 00/38000; WO 00/38001; WO 00/36560; WO 00/20922; WO 00/36666; WO 00/67110; WO 00/67327; WO 01/07961; WO 01/08241; WO 01/17029; and WO 01/17041. The entire disclosures of all these patents and published applications, all of which are in the name of, or assigned to, the Massachusetts Institute of Technology (MIT) or E Ink Corporation, are herein incorporated by reference.
Prior art electrophoretic displays use particles, which, while small (typically about 0.25 to 2 xcexcm), are sufficiently large that they have essentially the bulk properties of the material from which they are formed. The particles keep the same optical properties during the time they are present in the electrophoretic display; the appearance of the display is changed by moving the particles within the suspending fluid using an appropriate electrical field. For example, consider the prior art electrophoretic display represented in a schematic manner in FIG. 1 of the accompanying drawings. This display is provided on its front viewing surface (the top surface as illustrated in FIG. 1) with a common, transparent front electrode 100, and on its rear surface with an opaque substrate 102 carrying a matrix of discrete electrodes; only two of these electrodes, designated 104 and 106 respectively, are shown in FIG. 1. Each of the discrete electrodes 104 and 106 defines a pixel of the display. An encapsulated electrophoretic medium (generally designated 108) is disposed between the common electrode 100 and the discrete electrodes 104 and 106; for ease of illustration, FIG. 1 shows only a single capsule 110 of the medium 108 associated with each discrete electrode 104 and 106, although in practice a plurality of capsules (typically at least 20) would be associated with each discrete electrode. Also for ease of illustration, the capsules are shown in FIG. 1 as of circular cross-section, although in practice it is preferred that they have a flattened form.
Each of the capsules 110 comprises a capsule wall 112, a dark colored fluid 114 (assumed for present purposes to be blue) contained within this capsule wall 112 and a plurality of light colored charged particles 116 (assumed for present purposes to be titania particles 250-500 nm in diameter) suspended in the fluid 114. For purposes of illustration, it is assumed that the titania particles 116 are negatively charged so that they will be drawn to whichever of their associated discrete electrode and the common electrode is at the higher potential. However, the particles 116 could alternatively be positively charged. Also, the particles could be dark in color and the fluid 114 light in color so long as sufficient color contrast occurs as the particles move between the front and rear surfaces of the display medium, as shown in FIG. 1.
In the display shown in FIG. 1, each of the discrete electrodes is held at either 0 or +V (where V is a drive voltage) while the common front electrode 100 is held at an intermediate voltage +V/2. Since the titania particles 116 are negatively charged, they will be attracted to whichever of the two adjacent electrodes is at the higher potential. Thus, in FIG. 1, discrete electrode 104 is shown as being held at 0, so that the particles 116 within the adjacent capsule move adjacent the common electrode 100, and thus adjacent the top, viewing surface of the display. Accordingly, the pixel associated with discrete electrode 104 appears white, since light entering the viewing surface is strongly reflected from the titania particles adjacent this surface. On the other hand, discrete electrode 106 in FIG. 1 is shown as being held at +V, so that the particles 116 within the adjacent capsule move adjacent the electrode 106, and the color of the pixel associated with electrode 106 is that exhibited by light entering the viewing surface of the display, passing through the colored fluid 114, being reflected from the titania particles adjacent electrode 116, passing back through the colored fluid 114, and finally re-emerging from the viewing surface of the display, i.e., the associated pixel appears blue.
It should be noted that the change in the appearance of a pixel of this electrophoretic display as the voltage on the associated discrete electrode changes is solely due to the change of the position of the titania particles within the fluid; the color and other optical characteristics of the titania particles themselves do not change during operation of the electrophoretic display. In both the pixels shown in FIG. 1, the function of the titania particles is to scatter light strongly.
Obviously, the type of display shown in FIG. 1 can use particles of pigments other than titania, for example magenta pigments such as Hostaperm Pink E (Hoechst Celanese Corporation) and Lithol Scarlet (BASF), yellow pigments such as Diarylide Yellow (Dominion Color Company), cyan pigments such as Sudan Blue OS (BASF), and the like (see U.S. Pat. No. 5,364,726). However, in all cases the contribution of the pigment to the color of the display depends on the position of the pigment with respect to the viewer. When the pigment particles are adjacent the viewing surface of the display, the light scattered by the pigment is the color viewed. When the pigment is adjacent the rear surface of the display, the color is the color obtained when light passes through the fluid, is scattered from the pigment adjacent the rear surface, and then passes through the fluid again.
The single particle/color fluid type of electrophoretic display shown in FIG. 1 has two disadvantages. Firstly, the display can only produce two colors, in the manner already described, and is not capable of producing a wide range of colors. Secondly, to effect a change between the two color states, it is necessary for the titania particles to move under the electric field essentially the full distance between the two electrodes, and in practice this typically leads to a transition time between the two states of a few hundred milliseconds, and a frame rate of the order of 1 Hz or less, which is too slow for video applications.
Combinations of different colored pigments can be used in electrophoretic displays to form different colored images. If the different colored pigments are contained in the same volume of liquid, different colors are possible provided that the motion of each color of pigment under the influence of an electric field is different. For example, a mixture of white pigment particles positively charged and black pigment particles negatively charged could be used to make black on white or white on black images by application of X appropriates electric fields.
An electrophoretic display containing only two differently colored pigments is only capable of producing a few different colors: two when either color pigment is on the viewing side of the display, one when both pigments are on the viewing side of the display, and one when both pigments are on the back of the display. Such displays are not capable of producing a wide range of colors.
When the electrophoretic display contains just two colored pigments then the position of the colored pigments can be controlled if the colored pigments have electric charges of opposite polarity. With the electric field on with one polarity, the pigment of one color will migrate to the front of the display and the pigment of the other color will migrate to the back of the display. When the electric field is reversed, the pigments will exchange places, changing the color visible to the viewer. The time necessary to switch the color of the display is the time necessary for the pigment particles to diffuse under an applied electric field from one side of the display to the other, and is thus similar in magnitude to that of the electrophoretic display discussed above with reference to FIG. 1.
It is possible to construct an electrophoretic display composed of two different color pigments with the same polarity of charge but substantially different electrophoretic mobilities, if the electrophoretic mobility of one pigment is substantially different from that of the other. One appropriate addressing scheme is to pull all the particles to the rear of the display with the appropriate electric field. The reverse electric field is then applied only as long as it takes the more mobile of the two types of particles to reach the front viewing surface. This produces the color of the higher mobility particles. To produce the color of the lower mobility particles, all of the particles are pulled to the front of the display. Then, the field is reversed long enough that the more mobile particles are pulled away from the front electrode, leaving the lower mobility particles adjacent the front electrode. This produces the color of the lower mobility particles. The average time necessary to switch the color of the display is still at least the time necessary for the pigment particles to diffuse under an applied electric field from one side of the display to the other.
In theory, it would be possible to produce electrophoretic displays with a X multitude of different colored pigments dispersed in a fluid. If each colored pigment had its own distinct electrophoretic mobility, then a range of colors could be produced in a manner similar to that just described for an electrophoretic display composed of two colored pigments with the same sign, but different magnitudes of electrophoretic mobilities. However, two obvious problems are likely to render such media containing more than three or four colors extremely difficult to produce in-practice. All pigment dispersions, even of the same chemistry, have distributions of electrophoretic mobilities arising from a distribution of particle sizes, a distribution of particle charges, and a distribution of particle shapes. In order to control the image color with a multitude of different colored pigments, the distributions of electrophoretic mobilities for each color pigment would have to be substantially separated. This is a difficult challenge. Not only would the distributions of electrophoretic mobilities have to be substantially non-overlapping when the display was manufactured, they would have to remain substantially non-overlapping for the useful life of the display. Furthermore, the switching time necessary to switch the color of the display would still be at least as great as in the electrophoretic displays discussed above.
One approach to expanding the limited range of colors available from conventional electrophoretic displays is to place an array of colored filters over the pixels of the display. For example, the display shown in FIG. 1 could be modified by changing the color of the fluid 114 to black or gray instead of blue and then placing an array of color filters (say red, green and blue) over the individual pixels of the display. Moving the titania particles adjacent the viewing surface of a pixel covered with a red filter would color that pixel red, whereas moving the titania particles of the same pixel adjacent the rear surface of the display would render the pixel dark or black. The main problem with this approach to generating color is that the brightness of the display is limited by the pixelation of the color filter. For example, if a red color is desired, the pixels covered by red filters are set to appear red. whereas the pixels covered by green and blue filters are set to appear dark, so that only a fraction of the display surface has the desired color while the remaining portion is dark, thus limiting the brightness of any color obtained.
In encapsulated electrophoretic displays another method can be used to create different colored images, namely the different colored particles can be encapsulated in different microcapsules. Microcapsules containing each of the colors can be coated on top of the appropriate addressing electrodes so that the color of choice can be displayed by moving the pigment of that color in its capsule from the back of the display to the front while all the other color pigments in their own capsules are kept at the back of the display. This design suffers from one of the same limitations as the display using color filters. When a particular color pigment is moved to the viewing surface of the display and all the other colors are moved to the back of the display, then the display surface only shows the desired color over a fraction of its surface with all the other surface showing the background color. This limits the optical performance obtainable.
Thus, a common feature of all these prior art methods to create color in electrophoretic displays is that the different colors are created primarily by controlling the position of the particles in the display, that is the color is determined by whether any particular colored pigment particles are near the viewing surface of the display or near the back of the display. Also, the time necessary to change colors is the time necessary for particles to move under the influence of an applied electric field from one side of the display to the other, and this time is typically of the order of hundreds of milliseconds.
The present invention seeks to provide electrophoretic displays which can achieve a greater variety of colors than are possible in prior art displays. The present invention also seeks to provide electrophoretic displays with reduced switching times.
Accordingly, the present invention provides an electrophoretic display comprising a fluid and a plurality of nanoparticles having diameters substantially less the wavelengths of visible light such that, when the nanoparticles are in a dispersed state and uniformly dispersed throughout the fluid, the fluid presents a first optical characteristic, but when the nanoparticles are in an aggregated state in which they are gathered into aggregates substantially larger than the individual nanoparticles, the fluid presents a second optical characteristic different from the first optical characteristic, the electrophoretic display further comprising at least one electrode arranged to apply an electric field to the nanoparticle-containing fluid and thereby move the nanoparticles between their dispersed and aggregated states.
The present invention also provides a process for forming a nanoparticle assembly comprising a nanoparticle secured to an object via a linking group. This process comprises treating a nanoparticle with a linking reagent comprising the linking group and a first functional group capable of reacting with the nanoparticle under the conditions of the treatment, thereby causing the first functional group to react with the nanoparticle and secure the linking group to the nanoparticle. Thereafter the nanoparticle carrying the linking group is treated with a modifying reagent effective to generate a second functional group on the linking group, this second functional group being capable of reacting with the object. Finally, the nanoparticle carrying the linking group and the second functional group is contacted with the object under conditions effective to cause the second functional group to react with the object and thereby form the nanoparticle assembly.
The present invention also provides an electrophoretic display comprising a fluid, a plurality of a first species of nanoparticles in the fluid and a plurality of a second species of nanoparticles in the fluid, the first and second species of nanoparticles differing in electrophoretic mobility. The display has a viewing surface through which the nanoparticle-containing fluid can be viewed, and also has:
(a) a first display state in which the first and second species of nanoparticles are dispersed through the fluid;
(b) a second display state in which the first species of nanoparticles are aggregated and visible through the viewing surface; and
(c) a third display state in which the second species of nanoparticles are aggregated and visible through the viewing surface,
the first, second and third display states differing in at least one optical characteristic.
This type of display may hereinafter for convenience be called a xe2x80x9csingle layer displayxe2x80x9d of the invention.
The present invention also provides an electronic display comprising, in order, a light-transmissive first electrode forming a viewing surface; an electrophoretic medium comprising a plurality of nanoparticles in a light-transmissive fluid; a light transmissive second electrode; an electro-optic medium; and a third electrode. In this display, the electro-optic medium is capable of being switched between a first optical state and a second optical state by application of an electric field between the second and third electrodes. Thus, the electronic display has:
(a) a first display state in which the plurality of nanoparticles are dispersed through the fluid and the electro-optic medium is in its first optical state and visible through the viewing surface;
(b) a second display state in which the plurality of nanoparticles are dispersed through the fluid and the electro-optic medium is in its second optical state and visible through the viewing surface; and
(c) a third, display state in which the plurality of nanoparticles are aggregated and visible through the viewing surface,
the first, second and third display states differing in at least one optical characteristic.
This type of display may hereinafter for convenience be called a xe2x80x9cdouble layer displayxe2x80x9d of the invention.
This invention also provides a nanoparticle assembly comprising a nanoparticle having a diameter substantially less than the wavelengths of visible light, an object separate from the nanoparticle, and a flexible filament (or xe2x80x9ctetherxe2x80x9d) connecting the nanoparticle and the object, such that at least one optical characteristic of the nanoparticle varies with the spacing between the nanoparticle and the object.
Such nanoparticle/tether assemblies can be of several different types, including:
(a) a dual nanoparticle assembly, as shown in FIGS. 5A and 5B below, in which two nanoparticles are attached to opposed ends of a tether, which is typically a polymeric filament;
(b) a multiple nanoparticle assembly, in which a plurality of nanoparticles are attached via tethers to a central particle;
(c) nanoparticle/macroparticle assemblies, such as that shown in FIG. 8 below, in which a plurality of nanoparticles are attached via tethers to a macroscopic particle, which is typically an electrode; and
(d) a xe2x80x9cpolymer-dispersedxe2x80x9d nanoparticle assembly in which a plurality of nanoparticles and dispersed within (and optionally bonded to) a polymeric matrix or gel.
In one form of such nanoparticle assemblies, the optical characteristics of the assemblies are varied by changing the distances between nanoparticles; thus, in the nanoparticles assemblies of the aforementioned types, the tethers may function solely as mechanical devices to limit the movement of nanoparticles relative to each other, or to any macroparticle to which they are tethered. However, it has also been discovered that the optical characteristics of nanoparticle assemblies can be varied not only by changing the distance between the nanoparticles within the assembly, but also by changing the electrical conductivity of one or more tethers, and this invention extends to such xe2x80x9cvariable conductivityxe2x80x9d nanoparticle assemblies and to displays incorporating such assemblies.
Thus, this invention also provides a nanoparticle assembly comprising a nanoparticle, a second particle and a tether connecting the nanoparticle to the second particle, the tether having first and second states differing in electrical conductivity such that at least one optical characteristic of the nanoparticle assembly changes when the tether is varied from its first state to its second state.
This invention also provides an electro-optic medium comprising a plurality of such nanoparticle assemblies and means for varying the electrical conductivity of the tethers of the nanoparticle assemblies. In one form of such electro-optic medium, the nanoparticle assemblies are of the type having two nanoparticles joined by a tether, these nanoparticle assemblies being dispersed in a solvent or gel containing an electrolyte. A display of the present invention may be formed by providing such an electro-optic medium with a pair of electrodes on opposed sides of the medium, at least one of these electrodes being substantially transparent.
This invention also relates to a modification of the nanoparticle assemblies of type (b) discussed above, in which a plurality of nanoparticles are attached via tethers to a central particle. It has now been realized that if the central particle and the nanoparticles are given charges of opposite polarity, the tethers can be eliminated.
Thus, the present invention also provides an electro-optic medium comprising:
a suspending fluid;
a plurality of a first type of particle suspended in the suspending fluid, the first type of particle being light transmissive and bearing an electric charge; and
a plurality of a second type of particle suspended in the suspending fluid, the second type of particle being smaller than the first type of particle and bearing an electric charge of opposite polarity,
the particles being such that when no electric field is applied to the medium and the second type of particles lie on the surfaces of the first type of particles, the medium present a first optical characteristic, but when an electric field is applied to the medium and the second type of particles are removed from the surfaces of the first type of particles and dispersed through the suspending fluid, the medium present a second optical characteristic different from the first optical characteristic.
This type of medium may hereinafter for convenience be called a xe2x80x9ctether-less two particle mediumxe2x80x9d.
This invention also provides a nanoparticle assembly comprising a plurality of nanoparticles dispersed in a polymeric medium or gel, the medium or gel having first and second states differing in electrical conductivity such that at least one optical characteristic of the nanoparticle assembly changes when the medium or gel is varied from its first to its second state. In such a nanoparticle assembly, the nanoparticles may or may not be chemically bonded to the polymeric medium or gel.
This invention also provides a nanoparticle assembly comprising a plurality of nanoparticles and a polymer chain, the nanoparticles being spaced from one another along the polymer chain, the polymer having first and second conformations such that the distances between adjacent nanoparticles along the chain differ in the first and second conformations and at least one optical characteristic of the nanoparticle assembly differs between the first and second conformations.
Finally, this invention provides an improvement in a process in which a metal-containing ionic species is transferred from a aqueous phase to an organic phase using a phase transfer reagent, the ionic species subsequently being reduced to produce metal nanoparticles in the organic phase. The improvement comprises using a tetrabutylammonium halide, preferably the bromide, as the charge transfer reagent.